Iwao arai



Jan. 14, 1964 A V I00 Filed Marbh 15, 1961 Kg/cm INVENTOR IwAo Azai BY ATTORNEY United States Patent G 3,117,969 PRQCESS FER THE PRGDUCHON F MELAMEE lwao Aral, Toyama-ken, Japan, assignor to Nippon Carhide Kogyo Kahushilri Kaisha, Tokyo, Japan, a

corporation of .lapan Filed Mar. 15, 1961, Ser. No. 95,935 Claims priority, application Japan Feb. 7, 1961 2 Claims. (Cl. 260249.7)

Billfifi Patented Jan. id, 1964 monia gas, the pressure of the ammonia being at least 50 kg./cm. to a reaction temperature of above 300 C. but below the melting point of melamine as rapidly as possible.

By the study of the present inventor, it was revealed that in the production of melamine from liquid ammonia solution of dicyandiamide or cyanamide, there is a very close relationship between the reaction temperature and the degree of purity of the obtained melamine; and between the former and the amount of melam produced as the by-product.

As the illustration, if an example is given, when a solution wherein the weight ratio of dicyandiamide to liquid ammonia was 121.15 was treated in accordance with Example 1 which shall be described later but at various temperatures, and the contents of the main impurities in the obtained crude melamine were examined, the results were as shown in Table I below.

TABLE I Reaction Temp. C.) 270 280 290 3 310 3 i 320 330 340 Composition of Crude Melamine (Weight. percent): A h D/iclamine r 94. 35. 0 95. (3-96. 2 95. 8-05. 3 90- 95- 4 96- O- 9 90- 8-9/- 4 97. 98. 9 98. 12-08. 5 98. 3-98. 7 Melam 1. 6-2. 4 1. 4-2. 1 1. 2-l 7 1. 2-1. 6 0. 9-1. 4 0. 1. 0 0. 4-0. 7 0. 1-0. 3 below 0.1 Mcleni 1. 2-1. 7 1. 2-1. 7 1.2-1. 7 1. 2-1. 7 1. 2-1. 7 1. 2-1. 7 1. 2-1. 7 1. 1-1. 5 0. 8-1. 4 Animeline 0. 15-0. 4 0. 15-0. 4 0. 15-0. 4 0v -0- 4 0- 4 0. 15-0. 4 0. 15-0. 4 0. 1-0. 2 0. 1-0. 2

In the past many processes have been known for production of melamine, such as heating dicyandiamide to above its melting temperature, or heating liquid ammonia solution or" dicyandiamide or cyanamide. However in crude melamine, usually various impurities are contained such as melam, melem, amrneline, ammelide, and melon.

According to the present inventors study, it was found that among those impurities particularly melam has a very adverse effect on refining operation or resinification of melamine. The solubility of melam in Water, although is very low when cold, increases rapidly at a high temperature, when the melam content in melamine is above about 1.5%. Therefore the removal of melam in refining crude melamine by recrystallization from water becomes very difiicult, making it virtually impossible to heighten the purity of the recrystallized melamine over 99%. Again in producing melamine resin by reacting melamine with formalin, the melam present as an impurity impairs the stability of the aqueous solution of methylolmelamine or its precondensation product, and makes said solution milk white. Thus the presence of melam brings several disadvantages.

Usually the recrystallization from water is one of the most advantageous processes for refining crude melamine on an indusetrial scale. However, while other impurities present in crude melamine can be separated and removed with relative ease by recrystallization process, being extremely hard-soluble both to cold and hot water, melam is very difiicult to be removed, because its solubility in water, although is very small when cold, increases rapidly when the water is hot. Therefore if a process to produce crude melamine having particularly low melam content is perfected, it must be said that its industrial value is very high.

Accordingly, the object of the present invention is to provide a process for manufacture of melamine of high purity, particularly of low melam content, and moreover at high yield.

The other objects and advantages of the present invention will be apparent from the following descriptions.

in the present invention, the above object is accomplished by heating liquid ammonia solution of dicyandiamide and/ or cyanamide in an atmosphere of mainly am- As is apparent from the above Table I, while at the reaction temperature below 230 C. the by-produced melam content in the obtained crude melamine is about 15-20% and greater, the by-produced melam content decreases at a higher temperature, with a relative rapidity from up above 300 C. adopted in the present invention. Particularl at above 310 C. it can be seen the melam content is remarkably reduced.

In connection with the above result, the present inventor discovered a very interesting fact from another standpoint. That is, the present inventor obtained pure melam from a large amount of crude melamine by alkali treatment, and after confirming its identity by concurrent use of the ion-eXchange chromatography and the measurement of ultraviolet absorption curve, and also by elementary analysis and other methods, examined the behavior of melam under heating by subjecting the thu obtained melam to diiterential thermal analysis under superatmospheric pressure. As the result, a graph as in the attached drawing was obtained. Said differential thermal analysis was carried out in such a manner tha of the two sample containers in an autoclave of 450 cc. capacity, one was filled with 1.5 g. of melam and 19.0 g. of liquid ammonia, whfle the other, with about equal amount of alumina as control and also 19.0 g. of liquid ammonia, said autoclave being heated at the rate of 5 C./min. At 100 C. the pressure showed about 43 kg./cm. at 300 C., about 70 kg./cm. and at 350 C., about lrg./cm. The curve b in the attached drawing illustrates this pressure variation.

The exothermal value is shown by the curve a of the attached drawing. As can be understood from the behavior of the curve a, at a temperature above 300 C. a rapid evolution of heat was recognized forming a peak p in the drawing, and at about 340 C. the evolution of heat ceased.

Further, when the temperature was raised about to 345 C., an intense heat absorption started to take place, 1S shown by the valley q in the drawin And, the analysis of the reaction product confirmed the formation of melamine.

From the above data, it is presumed that the peak p apparently represents the heat evolved by the reaction of melam and ammonia to form melamine, and also that the valley at above 345 C. represents the heat of melting of melamine. Thus the fact that the formation of melamine from melam suddenly starts at 300 C. and higher perfectly corresponds with the phenomenon that from 390 C. upward the melam content of crude melamine rapidly decreases as shown in Table I.

Further it is as explained in the foregoing that when employment of the conventional recrystall zation proc- As is apparent from the above Table II, with the pressure in the reaction system of above 50 lig./cm. particularly above 55 lcg/ 0111. not only the degree of purity of the obtained crude melamine becomes high, but also its melarn content decreases rapidly, resulting in easy relining of the crude melamine and consequently, production or" melamine of high purity.

Again it has been already known in the production of melamine from liquid ammonia solution of dicyandiamide and/or cyanamide, that the high pressure of the amess from water, one of the industrially advantageous 19 pmgesges f m nuf t re, of rgfined l in ontainmonia gas in the autoclave results in increase of melamine ing above 99% pure melamine as is normal in the pure yield, the high pressure prollib g the side reaction, demelamine commercially available, is desired, the less is ammonization of melamine. the melam centen of tiifi crude melamine, the better. Thus, t maintain the PIESSP-YB Of 316 gas mainly of When the melam content of crude melamine becomes ammonia in the autoclave above 50 l g./cm. particubelow about 1.0%, the refining of the same by recrystallarly 55 kg/cm. as in this invention is a critical condilization process to obtain melamine of above 99% purity liOfl for manufacture 05 high P m'ilaminei as Such is rendered very easy. enables production of melamine at a high yield as well as Consequently, from the above standpoint it is parremarkable decrease in melam content, and moreover imticularly preferable to employ a reaction temperature of PTOWS i113 P y of lbs Cmda melaminfi- 310 C. or higher at the time of formation of melamine. Th6 PTeSeIll inventor also disciwfied that it is an 0 h m h d, 1 known l i point f pure portant requirement for production of crude melamine melamine being 354 C., that of crude melamine is usuof hig P y to heat the liquid ammonia solution of ally a little lower than that due to the presence or" in diCl/flndiflmide and/0r cyanamide With as much rapidity purities, and thus too high a temperature may cause sinterand niformi y as possible it) Elbow p ic l rly ing and solidification of the produced melamine as deabove blll below mailing 1mint of melaminescribed later, hindering the smooth progress of the opera- F i p p the most effective is to cause the ntion. Therefore it is desirable in normal circumstances fact of liq i ammonia Solution of dicyalldiamie and/OI to set the upper limit of the reaction temperatures emcyanaml'dfi with a heating medium of as great a h'iat ployed in the present invention at 345 C. pa ity as possible which is heated to a temperature above Further in the present invention it is as indicated by the desired reaction temperature, of course above 390 the results in Table I that among so specified reaction C., by jetting and contacting the ammonia solution against temperature ran e as above 360 C. but below melting said heating medium with suitable amount of flow. point of melamine, preferably 310 C.-345 C., as high As the heating medium, those having a great heat a temperature as feasible is particularly preferred, capacity and moreover high ICSlS'tlVliY t0 ammonia are Also the reason Why the reaction temperature is repreferred, such as iron, or an alloy thereof such as stainstricted as below melting point of melamine in this inless steel, or other metals or alloys. vention is that, with the reaction temperature of above In this invention, such heating medium may be promelting point of melamine, the melted product melamine Vided at a suitable place in the autoclave in the form is solidified when cooled, and adhered to the inside of the 49 of plate, rod, ball, or mass, or the inner wall of the autoautoclave when the same should be taken out, making clave may be used as the heating medium. And as althe taking-out operation very diflicult. Thus a temperaready mentioned, these heating media should be positure above melting point of melamine cannot be used intively heated to above the desired temperature, above dustrially from the practical standpoint. 300 C., by direct or indirect heating means such as elec- Again according to the study of the present inventor, tric heat, or Dowtherm. in a reaction to form melamine by rapidly heating liquid When liquid ammonia solution or dicyandiamide ammonia solution of dicyandiamide and/ or cyanamide as and/ or cyanamide is heated to above 300 C. but below in this inVeIlfiOn, accomPe-nyifig the increase of Pressure melting point of melamine rapidly and uniformly by bei i autoclave, e P mtllamifie cofllent 0f T116 Product r0 ing jetted against the inner surfaces of an autoclave which 15 Increased approxlmately 111 p pg m n the melam s been heated to above 300 c. and thus being concoment is decreased aPProxlmatfa'ly m P P F P tacted in accordance with the preferred mode of prac- El melen} Col/em m 3 Product is l fixphclfly ticing this invention, immediately after the starting of Influenced by me -5 OI pfessure as m ms case of the reaction the product melamine adheres and piles up melam, and moreover it was round that the ammelme r7 h er 0V th P f thp p1 content has substantially no relationship with pressure e 1 i O auto f t0 f Variation. said ammonia solution impinges. And, by the study of As an illustration, the relationship among the pressure f presfmt so adhsied f 'i Elf/6r prevellts condition, degree of purity of product crude melamine Le {391d and eatlng the; hluld amp-0111a and the melam, melem, and ammeline contents of said sohmon of dicyandlamlde and/OT cyanamide jailed crude melamine was examinfid as to thg case wherein the 69 against said layer, resulting in the lowering of the purity reaction i can-Rd out empicyjng the nditions f of the obtained crude melamine as well as increase in ample 1 as set forth later, but with various pressures of its Int/1am Content In Such a Case, lhsrfifma, higher P Y the ammonia gas in the autoclave arranged by controlling Crude melamine a be ta d y co s a tly scraping the discharge rate of ammonia gas from the autoclave. 6M oil the product melamine continuously adhering and pil- The results obtained were as shown in Table 11 below. ing up in layer on the surfaces of the heating medium TABLE 11 Reaction Pressure, kgJcm. 43 51 55 74 Composition of Crude Melamine (Weight peri /ielamine -2. 96.6 96. 5-915 98.0-98.5 98. -9s.5 1VIellJn 1. 0-1. 2 0. 7-0. 9 0. 1-0. s 0. 1-0. 2 Melem. 2. 5-3. 5 2. 0-3. 0 1. 2-1. 5 1.1-1. 5 Ammelino 0. 2-0. 3 0. 2-0. 3 0. 1-0. 2 0. l-O. 2

to which said solution is jetted, such as the inner surfaces of the autoclave, for example, by means of a stirrer.

Therefore, in practicing this invention industrially, an autoclave equipped with positive heating means to heat the inner surfaces of said autoclave, and also with a stirrer having Wings, preferably provided as close to said inner surfaces as possible, is advantageously used. The most preferred practice is such that the liquid ammonia solution of dicyandiamide and/or cyanamide is continuously jetted against said inner surfaces in an amount of flow as will not lower the temperature of said inner surfaces below 300 C., while the zone of said inner surfaces of the autoclave to which said ammonia solution impinges and the neighbouring zones thereto in the autoclave being maintained at a temperature above 300 C. but below melting point of melamine and the pressure of the gas mainly of ammonia gas in the autoclave being maintained above 50 kg./cm. particularly above 55 kg./cm.

Next the present invention shall be explained as to examples, it being understood that the following examples are given for only illustration purposes showing some examples of modes of practicing this invention, and that the present invention is by no means thereby limited.

Example 1 Eighty-one (-81) liters of liquid ammonia solution of dicyandiamide preheated to 130 C. in advance (dicyandiamide 30 kg liquid ammonia 35 kg.) were continuously fed at the flow rate of l./min. against the heated inner surfaces of an autoclave made of stainless steel having a capacity of 200 l. equipped with a heating jacket and scraper, preferably to the zone of said inner surfaces located apart from the zone whereon the produced melamine fell and piled up.

Meanwhile the ammonia atmosphere in the autoclave was constantly maintained at 70 kg./cm. by controlling the ammonia gas out-let valve, and by maintaining the Dowtherm in the heating jacket at 335345 C., the reaction temperature of conversion of fed dicyandiamide to melamine was kept at 330 C.i2 (2., care being taken that the heat of Dowtherm in the jacket should be conducted swiftly to the Zone where the dicyandiamide is being converted to melamine. Also by continuous operation of the scraper in the autoclave which is provided facing the inner surfaces at the clearance of average 2-3 mm., the adhering and piling up of melamine on the inner surfaces of the autoclave was prevented.

After all of the liquid ammonia solution of dicyandiamide was charged into the pressurized autoclave, the pressure of the autoclave was removed and the formed melamine was taken out. 29.5 kg. of the product was obtained.

Thus obtained crude melamine had a purity of 98.3%, and contained the by-produced impurities at such a ratio as: melam, 0.2%; melem, 1.3%; and ammeline, 0.13%.

Example 2 Under the similar conditions to those of Example 1 and by way of comparison, a solution comprising 30 kg. of dicyanidamide and 35 kg. of liquid ammonia was fed continuously to a similar autoclave, except that in this example the clearance between the scraper and the inner surfaces of the autoclave was extended to average 10-15 mm., thus permitting more melamine to pile up on the inner surfaces of the autoclave. 29.4 kg. of the product was obtained.

The product melamine of the above had a purity of 95.7%, and contained the by-produced impurities at such ratio as: melam, 2.0%; melem, 1.6%; and ammeline,

6 0.4%. This example illustrates that the additional amount of melamine adhering to the inner surfaces of the autoclave prevented proper heating of the ammonia solution and resulted in a poorer product.

Example 3 A similar autoclave equipped with a scraper as used? in Example 1 was charged with 81 liters of liquid am-: monia solution of dicyandiarnide comprising 30 kg. of dicyandiamide and 35 kg. of liquid ammonia, which had been preheated to C. in advance, at a flow rate of 3 l./ min. The reaction was carried out under the pressure of 60 kg./cm. of the ammonia gas.

In this reaction, the reaction temperature used was 325330 C., effected by maintaining the temperature of the Dowtherm in the jacket at 3 30340 C. When the feeding of all the ammonia solution of dicyandiamide was so completed under said pressure, the ammonia gas was discharged to lower the pressure, and the product was taken out. Thus obtained crude melamine had a purity of 98.0% and contained the by-produced impurities at such a ratio as: melam, 0.4%; melem, 1.4%; and ammeline, 0.15%.

Example 4 Three-hundred and sixty-five (365) liters of liquid ammonia solution of dicyandiamide comprising 122 kg. of dicyandiamide and 166 kg. of liquid ammonia, which had been preheated to C. in advance were reacted in the similar autoclave equipped with scraper as in Ex= ample 1, being fed at the flow rate of 3 l./ min. under the similar conditions as in Example 1 including the ammonia gas pressure.

The reaction temperature employed was 320330 C., effected by maintaining the temperature of the Dowtherm in the jacket at 335345 C.

After all the liquid ammonia solution of dicyandiamide was injected into the autoclave with pressure, the inner pressure of the autoclave was removed, and 120 kg. of the produced crude melamine were taken out.

The purity of the product was 97.5%, and impurities were present in such a ratio as: melam, 0.6%, melem, 1.4%; and ammeline, 0.4%.

After having set forth the gist of the present invention as in the foregoing, what the present inventor claims is:

1. A process for the production of melamine which comprises injecting a stream of a liquid ammonia solution of a compound selected from the group consisting of dicyandiamide and cyanamide into a heating zone against the surface of a hot, inert, solid medium in said heating zone, whereby said solution is rapidly heated to a temperature above about 300 C. but below the melting point of melamine, and solid melamine is formed on said heatcarrying solid medium surface, and continuously scraping said solid melamine off the surface of said heat-carrying solid medium, said heating zone containing an ammonia gas atmosphere maintained at a pressure of at least about 50 kg./cm.

2. The process according to claim 1 wherein said heat-- carrying solid medium is an inner wall of said heating zone.

References Cited in the file of this patent UNITED STATES PATENTS 2,164,705 Fisch July 4, 1939 2,170,491 Widmer et al Aug. 22, 1939 2,191,361 Widmer et al Feb. 20, 1940 FOREIGN PATENTS 314. 34 Gr at itain l n 1959 

1. A PROCESS FOR THE PRODUCTION OF MELAMINE WHICH COMPRISES INJECTING A STREAM OF A LIQUID AMMONIA SOLUTION OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF DICYANDIAMIDE AND CYANAMIDE INTO A HEATING ZONE AGAINS THE SURFACE OF A HOT, INERT, SOLID MEDIUM IN SAID HEATING ZONE, WHEREBY SAID SOLUTION IS RAPIDLY HEATED TO A TEMPERATURE ABOVE ABOUT 300*C. BUT BELOW THE MELTING POINT OF MELAMINE, AND SOLID MELAMINE IS FORMED ON SAID HEATCARRYING SOLID MEDIUM SURFACE OF SAID HEAT-CARRYING SOLID MEDIUM, SAID HEATING ZONE CONTAINING AN AMMONIA GAS ATMOSPHERE MAINTAINED AT A PRESSURE OF AT LEAST ABOUT 50 KG./CM.2. 